CN106366767A - Multifunctional water-based ink and preparing method thereof - Google Patents

Multifunctional water-based ink and preparing method thereof Download PDF

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Publication number
CN106366767A
CN106366767A CN201610748685.7A CN201610748685A CN106366767A CN 106366767 A CN106366767 A CN 106366767A CN 201610748685 A CN201610748685 A CN 201610748685A CN 106366767 A CN106366767 A CN 106366767A
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water
quantum dot
graphene
silver
graphene quantum
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陆庚
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Gaoming District Of Foshan City Is Runying Technology Co Ltd
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Gaoming District Of Foshan City Is Runying Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/52—Electrically conductive inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds

Abstract

The invention discloses a preparing method of multifunctional water-based ink. The preparing method includes the steps that 1, half of waterborne polyurethane resin, an antibacterial composite material and conducting filler are added into a reaction kettle and stirred uniformly, and an emulsifying agent is added dropwise; temperature raising, heat preservation and temperature lowering are carried out, a dispersing agent and water-based pigment are added, and pigment slurry is prepared through grinding after the mixture is stirred uniformly and is filtered; 2, remaining waterborne polyurethane resin, water, neutralizer, cosolvent and a defoaming agent are added into the pigment slurry, the mixture is dispersed through a grinding miller, and when the fineness reaches 5 micrometers or below, the mixture is packaged to obtain water-based ink. The conducting filler and the antibacterial composite material are reasonably matched, and therefore the ink has conductivity and durable antibacterial performance.

Description

A kind of multifunctional water-based ink and preparation method thereof
Technical field
The present invention relates to technical field of ink, a kind of more particularly to multifunctional water-based ink and preparation method thereof.
Background technology
With the enhancing of people's ecological awareness, the development and application of environment-friendly materials are increasingly taken seriously.Ink is just towards height Performance environment-friendly type direction is developed, and wherein, water color ink, based on water, is equipped with non-toxic water binder, not only cheap, printing Adaptability is good, and nontoxic, fragrant, safe, environmentally friendly, therefore extremely prints the favor on boundary.
During printing uses, it is poor that generation electrostatic is easily caused printing effect to ink.In order to reduce the danger that electrostatic is brought Evil, people add antisatic additive to suppress the generation of electrostatic charge and the leakage promoting electrostatic charge generally in ink, resist quiet Electric additive can reduce the resistance of ink, but the adhesive force of ink, brightness can reduce simultaneously, and printing effect is poor.
Content of the invention
The technical problem to be solved there is provided a kind of multifunctional water-based ink and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of multifunctional water-based ink, it comprises the following steps:
(1) take half waterborne polyurethane resin, antimicrobial composite material and conductive filler to add in reactor to stir, Deca breast Agent；It is warming up between 85 DEG C～90 DEG C, be incubated 1h；It is cooled to 30 ~ 40 DEG C, is initially charged dispersant, be subsequently adding aqueous pigment, Grind after stirring and prepare mill base, filter；
(2) remaining waterborne polyurethane resin, water, nertralizer, cosolvent are added in mill base, defoamer, in homogenizer Upper stirring 20 ~ 30min；At 30 ~ 40 DEG C, grinder disperses, and treats that fineness reaches less than 5 microns, and packaging obtains water color ink；Wherein,
Described water color ink is grouped into by the group of following weight proportion: 30～35 parts of waterborne polyurethane resin, aqueous pigment 30～ 35 parts, 20 ~ 25 parts of water, 5 ~ 10 parts of nertralizer, 1 ~ 3 part of emulsifying agent, 5 ~ 10 parts of dispersant, 0.1 ~ 0.5 part of defoamer, cosolvent 5 ~ 10 parts, 0.1 ~ 1 part of antibiotic complex and 0.1 ~ 1 part of conductive filler.
Described conductive filler is by porous carbon, CNT, white carbon black, graphene film, graphite and nanometer aluminium powder in mass ratio 4: 2:1:1:2:1 mixing composition；Described conductive filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water is added in 100ml water heating kettle, and sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, in 900 DEG C of air Calcine 1h under atmosphere, obtain porous carbon；CNT, nanometer aluminium powder, nano-graphite are dispersed in the aqueous solution of 120ml, leaching Enter porous carbon 1 ~ 2h, allow nano material well in duct, then sucking filtration；The filter cake of sucking filtration gained be immersed in 50ml white carbon black and In graphene film aqueous solution, 30 ~ 60min, then sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, in vacuum Under the conditions of 120 DEG C drying, obtain final product conductive filler.
Described cosolvent is ethanol, propanol or methoxy triglycol.
Described nertralizer is soda, ethanolamine, trimethylamine groups propanol or Diethylaminoethanol.
Described emulsifying agent is polyvinyl alcohol or sodium alkyl sulfonate.
Described dispersant is sodium polyacrylate, polyoxyethylene glycol Arrcostab or silicate.
Described defoamer is alkylphenol polyoxyethylene.
In the present invention, a kind of preparation method of antimicrobial composite material comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation Speed) 50 ~ 60ml graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction Temperature is 45 ~ 60 DEG C, and Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 60 ~ 120min；Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000w ultrasonic power, 300 ~ 500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon (mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(4) 0.1 ~ 0.3mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added Enter in 1 mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, heats up To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, cleaning, be dried, obtain carrying silver/ Titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~ In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ 0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) and be configured to the graphite that concentration is 0.2 ~ 0.8mg/ml Alkene dispersion soln, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w ultrasonic power, 600 ~ 800rpm stirs ultrasonic agitation Mix speed) 80 ~ 100ml graphene dispersion solution, add the load silver/titanium dioxide graphene quantum dot that step (5) is obtained, ultrasonic Stirring 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, Cleaning, dries to obtain antimicrobial composite material.
The invention has the following beneficial effects:
Conductive filler used in the present invention makes the conductive structure of ink finer and close, forms good interlayer UNICOM structure, conductive Passage is more smooth, thus improving conductivity and stability further, overcomes pure carbon black conductive ink electric conductivity not again Stable defect；And antimicrobial composite material is compounded with the anti-microbial property of silver particles and titanium dioxide, compared to single Yin Na Nano antibacterial agent has more preferable antibacterial effect, and antibacterial is lasting；By conductive filler and antimicrobial composite material carry out reasonably combined so that Ink not only has conductive characteristic, also has lasting anti-microbial property.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, It is not limitation of the invention.
Embodiment 1
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 5h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 30min simultaneously, swashs Photoirradiation power is 2w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 50ml Graphene quantum dot suspension, Deca concentration is 0.005mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration For 0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.1g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(4) 0.3mol/l titanium source (titanium source is potassium fluotitanate) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus Enter the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts ph with concentrated ammonia solution It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005g graphite oxide is added to dividing of 10ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.3g to carry silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 200w, at 240 DEG C react 60min；Cooling, filters, dries The load silver/titanium dioxide graphene quantum dot of surface treatment.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) be configured to concentration be 0.2mg/ml Graphene divide Scattered solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml Graphene dispersion solution, the load silver/titanium dioxide graphene quantum dot that addition step (5) is obtained, ultrasonic agitation 30min, then Move in the reactor of politef, be incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antibacterial composite wood Material.
Embodiment 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.6g c60 powder, measure 50 ~ 100ml mass fraction be 98% dense Sulphuric acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains Mixed liquor；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water 30 ~ 40 DEG C of bath temperature, reacts 7h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously 45min, laser irradiation power is 1.2w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml Graphene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration For 0.05mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(4) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus Enter the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table The load silver/titanium dioxide graphene quantum dot that face is processed.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) be configured to concentration be 0.5mg/ml Graphene divide Scattered solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml stone Black alkene dispersion soln, adds the load silver/titanium dioxide graphene quantum dot that step (5) is obtained, ultrasonic agitation 30min, Ran Houyi To the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g c60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 0.5g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water 30 ~ 40 DEG C of bath temperature, reacts 8h；Rapidly join 100ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously 60min, laser irradiation power is 1w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 50ml Graphene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration For 0.01mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(4) 0.1mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added to In 1 mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 110 DEG C, after reaction 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide Graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.01g graphite oxide is added to the dispersion of 5ml In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to carry silver/titanium dioxide Graphene Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface The load silver/titanium dioxide graphene quantum dot processing.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) be configured to concentration be 0.8mg/ml Graphene divide Scattered solution, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml Graphene dispersion solution, the load silver/titanium dioxide graphene quantum dot that addition step (5) is obtained, ultrasonic agitation 30min, then Move in the reactor of politef, be incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antibacterial composite wood Material.
Comparative example 1
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps: weighs porous Graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) is configured to the graphene dispersion solution that concentration is 0.8mg/ml, and solvent is water, acetone Or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, Deca is dense Spend for 0.001mol/l silver nitrate solution, controlling reaction temperature is 50 DEG C, Deca concentration is 0.01mol/l bis- citric acid monohydrate three Sodium, continues ultrasonic agitation 90min；Ageing, cleaning, dry to obtain antimicrobial composite material.
Comparative example 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) compound concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca concentration is 0.01mol/l Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, silver nitrate solution is 2:1 with the volume ratio of two citric acid monohydrate trisodiums；Afterwards Add water and the ammonia of volume ratio 3:1, be stirring evenly and then adding into tetraethyl orthosilicate, the quality with the graphene quantum dot of load silver For 1:1, adjust ph value is 9 ~ 10 to ratio, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；It is centrifuged and successively with acetone and going Ionized water cleaning obtains precipitation；This is deposited in 90o3h is dried, to obtain ag/sio under c2；
(2) 0.1mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added to 1 In mol/l sulfuric acid solution, mix homogeneously；Add the ag/sio that step (1) is obtained2, it is warming up to 110 DEG C, after reaction 4h, use dense ammonia Aqueous solution adjusts ph value to 7, after being aged 6 hours, cleans, is dried, obtains ag/sio2/ titanium dioxide；
(3) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm) be configured to concentration be 0.8mg/ml graphene dispersion molten Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphite Alkene dispersion soln, adds the ag/sio that step (3) is obtained2/ titanium dioxide, ultrasonic agitation 30min, then move to politef Reactor in, at 100 DEG C be incubated 30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
The detailed process that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated and step are as follows:
The antibacterial of test is respectively staphylococcus aureuses and escherichia coli；With reference to minimal inhibitory concentration (minimal Inhibitory concentration, mic) method of testing (xiang cai, shaozao tan, aili yu, jinglin zhang, jiahao liu, wenjie mai, zhenyou jiang. sodium1- naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver nanoparticles with lower cytotoxicity and long-term antibacterial Activity.chemistry-an asian journal. 2012,7 (7): 1664-1670.), first weighed with electronic balance Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with mh meat soup to serial dilute again Release variable concentrations, be added separately in the mh culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/ml, Then shaken cultivation 24h at 37 DEG C, observes as a result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, no The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (mic) for this antibacterial with the antibacterial of not long tube.
Table 1: the anti-microbial property of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, add prepared by each embodiment of 1g and comparative example in bottle Antimicrobial composite material sample and 200ml saline (0.9mass%), and soak 6 respectively in water, 24, sample after 72h, measure it Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Embodiment 4
A kind of preparation method of multifunctional water-based ink, it comprises the following steps:
(1) 16 parts of waterborne polyurethane resins, the antimicrobial composite material of 0.1 part of embodiment 2 and 1 part of conductive filler is taken to add reactor Inside stir, 2 parts of polyvinyl alcohol of Deca；It is warming up between 85 DEG C～90 DEG C, be incubated 1h；It is cooled to 30 DEG C, be initially charged 8 parts and gather Sodium acrylate, is subsequently adding 32 parts of aqueous pigments, grinds and prepare mill base after stirring, and filters；
(2) 16 parts of waterborne polyurethane resins, 25 parts of water, 8 parts of trimethylamine groups propanol, 0.2 part of alkyl phenol polyoxy are added in mill base Vinyl Ether, 5 parts of ethanol, stir 20 ~ 30min on homogenizer；At 30 ~ 40 DEG C, grinder disperses, and treats that fineness reaches 5 micro- Rice is following, packaging, obtains water color ink；Wherein,
Described conductive filler is by porous carbon, CNT, white carbon black, graphene film, graphite and nanometer aluminium powder 4:2:1 in mass ratio: 1:2:1 mixing composition；Described conductive filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water It is added in 100ml water heating kettle, sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, under 900 DEG C of air atmosphere Calcining 1h, obtains porous carbon；CNT, nanometer aluminium powder, nano-graphite are dispersed in the aqueous solution of 120ml, immerse porous Carbon 1 ~ 2h, allows nano material well in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black aqueous solution In, 30 ~ 60min, then sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, 120 DEG C of bakings under vacuum Dry, obtain final product conductive filler.
Embodiment 5
Based on the preparation method of embodiment 4, difference is: antimicrobial composite material is 0.3 part and 0.5 part of conductive filler.
Embodiment 6
Based on the preparation method of embodiment 4, difference is: antimicrobial composite material is 1 part and 0.1 part of conductive filler.
Comparative example 3
Based on the preparation method of embodiment 4, difference is: described antibiotic complex is nano silver antimicrobials.
Comparative example 4
Based on the preparation method of embodiment 4, difference is: described conductive filler is Graphene, white carbon black and copper powder with weight Mix than 6:1:4.
The carrying out of embodiment 4 ~ 6 and comparative example 3,4 is tested, result is as follows:
Antibacterial Evaluation for Uniformity: by ink even application on glass or ceramic wafer, choose 100 regions and carry out sterilizing test, Uniformity Analysis are carried out to the data recording, by the uniformity=100* (1- standard deviation/meansigma methodss).When the uniformity is more than 97%, then be labeled as ▲；When the uniformity is more than 90% and is less than 97%, then it is labeled as ☆；When the uniformity is less than 90%, then it is labeled as ╳.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation Art scheme, all should fall within the scope and spirit of the invention.

Claims (9)

1. a kind of preparation method of multifunctional water-based ink, it comprises the following steps:
(1) take half waterborne polyurethane resin, antimicrobial composite material and conductive filler to add in reactor to stir, Deca breast Agent；It is warming up between 85 DEG C～90 DEG C, be incubated 1h；It is cooled to 30 ~ 40 DEG C, is initially charged dispersant, be subsequently adding aqueous pigment, Grind after stirring and prepare mill base, filter；
(2) remaining waterborne polyurethane resin, water, nertralizer, cosolvent are added in mill base, defoamer, in homogenizer Upper stirring 20 ~ 30min；At 30 ~ 40 DEG C, grinder disperses, and treats that fineness reaches less than 5 microns, and packaging obtains water color ink；Wherein,
Described water color ink is grouped into by the group of following weight proportion: 30～35 parts of waterborne polyurethane resin, aqueous pigment 30～ 35 parts, 20 ~ 25 parts of water, 5 ~ 10 parts of nertralizer, 1 ~ 3 part of emulsifying agent, 5 ~ 10 parts of dispersant, 0.1 ~ 0.5 part of defoamer, cosolvent 5 ~ 10 parts, 0.1 ~ 1 part of antibiotic complex and 0.1 ~ 1 part of conductive filler.
2. the preparation method of multifunctional water-based ink according to claim 1 is it is characterised in that described conductive filler is by many Hole carbon, CNT, white carbon black, graphene film, graphite and nanometer aluminium powder 4:2:1:1:2:1 in mass ratio mixing composition；Described lead Electric filler preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added in 100ml water heating kettle, Sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, calcines 1h under 900 DEG C of air atmosphere, obtains porous carbon；Will CNT, nanometer aluminium powder, nano-graphite are dispersed in the aqueous solution of 120ml, immerse porous carbon 1 ~ 2h, make nano material abundant Enter in duct, then sucking filtration；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene film aqueous solution, 30 ~ 60min, Then sucking filtration again；The filter cake distilled water wash of sucking filtration gained again, 120 DEG C of drying, obtain final product conduction and fill out under vacuum Material.
3. the preparation method of multifunctional water-based ink according to claim 1 is it is characterised in that described antimicrobial composite material Preparation method as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, Deca silver nitrate Solution, controlling reaction temperature is 45 ~ 60 DEG C, Deca, continues ultrasonic agitation 60 ~ 120min；Ageing, cleaning, dry and must load silver Graphene quantum dot；
(2) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3 Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried, obtain sio2The stone of the load silver of cladding Black alkene quantum dot；
(3) 0.1 ~ 0.3mol/l titanium source is added in 1 mol/l sulfuric acid solution, mix homogeneously；Step (2) is added to be obtained sio2Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, old Change, cleaning, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) carry the surface treatment of silver/titanium dioxide graphene quantum dot；
(5) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) is obtained Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C insulation 15 ~ 30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
4. the preparation method of multifunctional water-based ink according to claim 3 is it is characterised in that described graphene quantum dot The preparation method of suspension is as follows: weighs 0.5 ~ 0.8g c60 powder, measures the concentrated sulphuric acid that 50 ~ 100ml mass fraction is 98%, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, stirred with the speed of 300 ~ 500rpm simultaneously, obtain Mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, protect 30 ~ 40 DEG C of water holding bath temperature, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then use molecular cut off to be 1000 Bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, swashs simultaneously Photoirradiation 30 ~ 60min, laser irradiation power is 1 ~ 2w.
5. the preparation method of multifunctional water-based ink according to claim 3 is it is characterised in that described porous graphene is 2 ~ 5 layers, the porous graphene of hole size about 3 ~ 6nm.
6. the preparation method of multifunctional water-based ink according to claim 3 is it is characterised in that described load silver/titanium dioxide The surface treatment of titanium graphene quantum dot, particularly as follows: being added to 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10ml, surpasses Sound stirs and adds 0.1 ~ 0.3g to carry silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moving to liner is In the microwave hydrothermal reaction kettle of politef, be placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power be 200 ~ 400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, dries the load silver/titanium dioxide Graphene amount that must be surface-treated Sub- point.
7. a kind of multifunctional water-based ink is it is characterised in that described water color ink is grouped into by the group of following weight proportion: aqueouss 30～35 parts of polyurethane resin, 30～35 parts of aqueous pigment, 20 ~ 25 parts of water, 5 ~ 10 parts of nertralizer, 1 ~ 3 part of emulsifying agent, dispersant 5 ~ 10 parts, 0.1 ~ 0.5 part of defoamer, 5 ~ 10 parts of cosolvent, 0.1 ~ 1 part of antibiotic complex and 0.1 ~ 1 part of conductive filler.
8. multifunctional water-based ink according to claim 7 is it is characterised in that described conductive filler is received by porous carbon, carbon Mitron, white carbon black, graphene film, graphite and nanometer aluminium powder 4:2:1:1:2:1 in mass ratio mixing composition.
9. multifunctional water-based ink according to claim 8 is it is characterised in that described conductive filler preparation method is as follows: By 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added in 100ml water heating kettle, seal anti-in 180 DEG C of baking ovens Answer 10h, after cleaned drying, calcine 1h under 900 DEG C of air atmosphere, obtain porous carbon；By CNT, nanometer aluminium powder, Nano-graphite is dispersed in the aqueous solution of 120ml, immerses porous carbon 1 ~ 2h, allows nano material well in duct, then take out Filter；The filter cake of sucking filtration gained is immersed in 50ml white carbon black and graphene film aqueous solution, 30 ~ 60min, then sucking filtration again；Again The filter cake distilled water wash of sucking filtration gained, 120 DEG C of drying, obtain final product conductive filler under vacuum.
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CN115521685A (en) * 2022-10-08 2022-12-27 北京星驰恒动科技发展有限公司 Coating, preparation method of coating and space cabin
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Application publication date: 20170201